Concentration and Composition of Atmospheric Aerosols from the 1995 SEAVS Experiment and a Review of the Closure between Chemical and Gravimetric Measurements

ABSTRACT

We summarize the results from the various measurements and the inter-sampler comparisons from Southeastern Aerosol and Visibility Study (SEAVS), a study with one of its objectives to test for closure among chemical, gravimetric and optical measurements of atmospheric aerosol particles. Sulfate and organics are the dominant components of the SEAVS fine particles (nominally, particles with aerodynamic diameter <2.5 u,m) but between 28 and 42% (range over various samplers) of the gravimetrically measured total fine particle concentration is unidentified by the chemical measurements. Estimates of water associated with inorganic components and measurement imprecision do not totally explain the observed difference between gravimetric and chemical measurements. We examine the theoretical and empirical basis for assumptions commonly made in the published literature to extrapolate total fine particle concentration on the basis of chemical measurements of ions, carbon and elements.     

A simplified approach to the indirect evaluation of the chemical composition of atmospheric aerosols from PM mass concentrations

The present work shows a straightforward procedure to indirectly estimate the chemical composition at a given site only from the determination of the PM concentrations, and the classification of the days according to the main meteorological scenarios. A previous study based on the mean chemical composition associated to the main meteorological scenarios is required.This experiment has been carried out with data from two monitoring sites in the North-Western Mediterranean, one regional and one suburban background. At both sites, one-year datasets on chemical PM₁₀ composition were obtained. Based on these datasets, the mean PM₁₀ compositions according to the most relevant meteorological situations were calculated for both locations. After that, the reconstruction of the chemical composition for all the days with available PM₁₀ concentrations was completed. Subsequently, the estimated PM₁₀ composition was compared with that determined experimentally. The comparison between the rebuilt and the experimental results was very satisfactory in the case of the regional background site, and relatively replaced in the other case. Furthermore, the validation of the method at the regional background site has been conducted from the reconstruction of a 4-year data base, and subsequent comparison with the experimental chemical composition.Our results show that it is possible to attain a good approach to the chemical composition at regional background sites, where local emission sources are negligible. Conversely, when the local sources rise in importance, i.e., at a suburban background site, the approach is suitable only for those components with a more regional origin and/or those from long range transport of air masses.     

Characterization of chemical species in atmospheric aerosols in a metropolitan basin

Ambient PM10 aerosol samples were collected from Taiwan's Taichung metropolitan basin between October 1997 and January 1998, and their chemical characteristics studied. The average mass concentration of PM10 was 109.0 +/- 54.1 microg/m3. Carbonaceous materials, sulfate, nitrate, and ammonium were the most important contributors to the PM10 component. On average, 64% of the PM10 was made up of fine particles. During PM10 episodes, average wind speed was 0.7 m/s and relative humidity was high, 83% on average, probably giving rise to stagnation of air pollutants and their entrapment close to the surface. With relative humidity < 70%, NO3-, NH4+, SO4(2-), carbonaceous materials, and PM10 mass showed high correlation with maximum hourly average ozone (O3M). Variation in atmospheric humidity may affect the gas-to-particle interactions of S and N species. The most significant contribution to PM10 in the Taichung urban basin was from the photochemical formation of secondary aerosols and carbonaceous materials in the atmospheric environment.     

大气超细颗粒物观测和扩散模拟研究进展

总结了近年来不同地区对不同环境下大气超细颗粒物的观测和扩散模拟研究进展。大量的观测研究结果表明,大气超细颗粒物的时空分布、组成特征、形成和成长的特性因观测地区的不同而存在很大差异,受气象因素和局部污染源的影响很大;其来源主要包括固定、移动燃烧源的直接排放和大气中颗粒成核现象,前一种来源一般是局部的,而后一种来源则是区域性的。目前,大多数关于大气超细颗粒物扩散的模拟研究都是针对其质量浓度的,对其数浓度扩散的模拟研究主要集中在小范围(机动车排放烟云的研究方面),在城市区域范围上的研究和应用还很少。最后,探讨和展望了大气超细颗粒物今后的主要研究方向和研究中面临的挑战。     

Composition and effects of inhalable size fractions of atmospheric aerosols in the polluted atmosphere: Part I. PAHs,PCBs and OCPs and the matrix chemical composition

Atmospheric particulate matter (PM) abundance, mass size distribution (MSD) and chemical composition are parameters relevant for human health effects. The MSD and phase state of semivolatile organic pollutants were determined at various polluted sites in addition to the PM composition and MSD. The distribution pattern of pollutants varied from side to side in correspondence to main particle sources and PM composition. Levels of particle-associated polycyclic aromatic hydrocarbons (PAHs) were 1–30 ng m^?3 (corresponding to 15–35 % of the total, i.e., gas and particulate phase concentrations), of polychlorinated biphenyls (PCBs) were 2–11 pg m^?3 (4–26 % of the total) and of DDT compounds were 2–12 pg m^?3 (4–23 % of the total). The PM associated amounts of other organochlorine pesticides were too low for quantification. The organics were preferentially found associated with particles <0.45 μm of aerodynamic equivalent diameter. The mass fractions associated with sub-micrometer particles (PM_0.95) were 73–90 %, 34–71 % and 36–81 % for PAHs, PCBs and DDT compounds, respectively. The finest particles fraction had the highest aerosol surface concentration (6.3–29.7)_×10^?6 cm^?1 (44–70 % of the surface concentration of all size fractions). The data set was used to test gas-particle partitioning models for semivolatile organics for the first time in terms of the organics' MSD and size-dependent PM composition. The results of this study prove that at the various sites particles with diverse size, matrix composition, amount of contaminants and toxicological effects occur. Legislative regulation based on gravimetric determination of PM mass can clearly be insufficient for assessment.     

Sources and chemical composition of atmospheric fine and coarse particles in the Helsinki area

During April 1996–June 1997 size-segregated atmospheric aerosol particles were collected at an urban and a rural site in the Helsinki area by utilising virtual impactors (VI) and Berner low-pressure impactors (BLPI). In addition, VI samples were collected at a semi-urban site during October 1996–May 1997. The average PM_2.3 (fine particle) concentrations at the urban and rural sites were 11.8 and 8.4 μg/m³, and the PM_2.3−15 (coarse particle) concentrations were 12.8 and about 5 μg/m³, respectively. The difference in fine particle mass concentrations suggests that on average, more than one third of the fine mass at the urban site is of local origin. Evaporation of fine particle nitrate from the VI Teflon filters during sampling varied similarly at the three sites, the average evaporation being about 50–60%.The average fine particle concentrations of the chemical components (25 elements and 13 ions) appeared to be fairly similar at the three sites for most components, which suggests that despite the long-range transport, the local emissions of these components were relatively evenly distributed in the Helsinki area. Exceptions were the average fine particles Ba, Fe, Sb and V concentrations that were clearly highest at the urban site pointing to traffic (Ba, Fe, Sb) and to combustion of heavy fuel oil (V) as the likely local sources. The average coarse particle concentrations for most components were highest at the urban site and lowest at the rural site.Average chemical composition of fine particles was fairly similar at the urban and rural sites: non-analysed fraction (mainly carbonaceous material and water) 43% and 37%, sulphate 21% and 25%, crustal matter 12% and 13%, nitrate 12% and 11%, ammonium 9% and 10% and sea-salt 2.5% and 3.2%, respectively. At the semi-urban site also, the average fine particle composition was similar. At the urban site, the year round average composition of coarse particles was dominated by crustal matter (59%) and the non-analysed components (28%, mainly carbonaceous material and water), while the other contributions were much lower: sea-salt 7%, nitrate 4% and sulphate 2%. At the rural site, the coarse samples were collected in spring and summer and the percentage was clearly lower for crustal matter (37%) and sea-salt (3%) but higher for the not-analysed fraction (51%). At the semi-urban site, the average composition of coarse particles was nearly identical to that at the urban site.Correlations between the chemical components were calculated separately for fine and coarse particles. In urban fine particles sulphate, ammonium, Tl, oxalate and PM_2.3 mass correlated with each other and originated mainly from long-range transport. The sea-salt ions Na⁺, Cl⁻ and Mg²⁺ formed another group and still another group was formed by the organic anions oxalate, malonate, succinate, glutarate and methane sulphonate. Ni and V correlated strongly pointing to combustion of heavy fuel oil as the likely source. In addition, some groups with lower correlations were detected. At the rural and semi-urban sites, the correlating components were rather similar to those at the urban site, although differences were also observed.     

The chemical composition of tropospheric aerosols and their contributing sources to a continental background site in northern Zimbabwe from 1994 to 2000

Atmospheric aerosols were collected in separate coarse (2–10 μm diameter) and fine (diameter less than 2 μm) size fractions at Rukomechi Research Station (16.1°S, 29.4°E), Zimbabwe, in the central part of southern Africa, from September 1994 to January 2000. The samples were analysed for the particulate mass (PM), black carbon, and 47 elements. The overall data set and the separate wet and dry season data sets were examined with absolute principal component analysis (APCA). Natural and anthropogenic aerosol sources were identified in both seasons, but the sources and their contributions to the total PM were found to vary between seasons and between size fractions. Crustal matter, sea salt (SS), a mixed biogenic (BIO) emission/biomass burning (BB) component, and a copper component were identified for the coarse aerosols during the wet season. APCA attributed 29% of the total wet season coarse PM to the mixed BIO/BB component, and 32% to SS. The copper component is likely due to the copper smelters in the Zambian Copperbelt. The dry season coarse PM originated from crustal matter, BB, BIO, and SS sources, with the major contribution (32%) coming from BB. Four components (crustal matter, BB, non-ferrous smelters, and SS) were identified for the fine particles for both the wet and dry seasons. The BB component provided the major contribution to the total fine PM, accounting for 44% and 79% in the wet and dry seasons, respectively. The relative contributions to the total PM (both fine and coarse) for all sources were greater in the dry season than the wet season, except for SS.     

Climatology of PM2.5 organic carbon concentrations from a review of ground-based atmospheric measurements by evolved gas analysis

In this work we have compared ground-based measurements of organic carbon (OC) in the fine aerosol (PM2.5) fraction that are reported in peer-reviewed publications as part of both short campaigns and continuous monitoring networks. The comparison provides a quantitative review of global OC measurements for the purpose of establishing the extent to which organic aerosol concentrations are known with sufficient geographic and historical resolution to constrain global climate models. Only North America has sufficient measurements to provide meaningful spatial and temporal trends, although available measurements from China and Japan indicate that the Asian region is the most polluted with OC concentrations of approximately 10 μg m^?3. These measurements have a low spatial resolution, with most sites located in highly urban areas within a small geographic region. OC concentrations in North America are approximately 1 μg m^?3 and are better characterized spatially, temporally, and historically by continuous monitoring networks established decades ago. OC concentration shows a weakly increasing trend in some regions from 1997 to 2006, although in most regions it has remained effectively constant over the last ten years. Eastern U.S. sites show maximum OC in the winter and western U.S. sites show maximum OC in the summer. There is no correlation at U.S. sites between OC concentration and sulfate, nitrate, or ammonium ions, with R² < 0.1 in each case.     

Mapping green technologies literature published between 1995 and 2019: a scientometric review from the perspective of the manufacturing industry

Environmental Science and Pollution Research - This study presents a comprehensive literature review and gives an insight into the increasing research trends that are based on the discipline of...     

Quantitative chemical composition and characteristics of aerosols over western India: One-year record of temporal variability

One-year quantitative chemical data set consisting of water-soluble constituents (NH₄⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺, Cl^?, NO₃^?, SO₄^2? and HCO₃^?), crustal and trace elements (Al, Fe, Ca, Mg, K, Mn, Zn, Pb) and carbonaceous species (OC, EC) in ambient aerosols, collected over an urban site located in a high-dust semi-arid region of western India, reveals excellent linear relationship (r² = 0.92; slope = 0.96 ± 0.05) between gravimetrically assessed TSP (total suspended particulates) and chemically analyzed aerosol mass. The TSP abundance ranging from 60 to 250 μg m^?3, over a period of 12 months (January–December), is dominated by mineral dust (～70%); whereas contribution from sea-salts, anthropogenic and carbonaceous species exhibits significant temporal variability depending upon the wind regimes. The mineral dust is enriched in Ca, Mg and Fe with respect to upper continental crust (UCC); whereas Zn and Pb exhibit a characteristic anthropogenic source and high enrichment factors. The carbonaceous species show significant seasonality; with dominance of OC (range: 4.6–28 μg m^?3; average: 12.8 μg m^?3; SD: 6.8) and minor contribution from EC (range: 0.3–4.4 μg m^?3; average: 2.4 μg m^?3; SD: 1.4). The observed concentrations are significantly lower than those reported for the metro cities in South Asia but the OC/EC ratios (range: 4.3–35; average: 8.3; SD: 5.7) are significantly higher than the characteristic ratio (～2–4) reported for the urban atmosphere. Such quantitative chemical characterization of aerosols is essential in assessing their role in atmospheric chemistry and climate change. This study could also be useful in understanding the physical and optical aerosol properties documented from the same site and thus, in validating regional climate models.     

Probing the sensitivity of gaseous Br2 production from the oxidation of aqueous bromide-containing aerosols and atmospheric implications

This paper presents a global sensitivity and uncertainty analysis of the bromine chemistry included in the Model of Aqueous, Gaseous and Interfacial Chemistry (MAGIC) in dark and photolytic conditions. Uncertainty ranges are established for input parameters (e.g. chemical rate constants, Henry's law constants, etc.) and are used in conjunction with Latin hypercube sampling and multiple linear regression to conduct a sensitivity analysis that determines the correlation between each input parameter and model output. The contribution of each input parameter to the uncertainty in the model output is calculated by combining results of the sensitivity analysis with input parameters' uncertainty ranges. Model runs are compared using the predicted concentrations of molecular bromine since Br_2(g) has been shown in previous studies to be generated via an interface reaction between O_3(g) and Br_(surface)^? during dark conditions [Hunt et al., 2004]. Formation of molecular bromine from the reaction of ozone with deliquesced NaBr aerosol: evidence for interface chemistry. Journal of Physical Chemistry A 108, 11559–11572]. This study also examines the influence of an interface reaction between OH_(g) and Br_(surface)^? in the production of Br_2(g) under photolytic conditions where OH_(g) is present in significant concentrations. Results indicate that the interface reaction between O_3(g) and Br_(surface)^? is significant and is most responsible for the uncertainty in MAGICs ability to calculate precisely Br_2(g) under dark conditions. However, under photolytic conditions the majority of Br_2(g) is produced from a complex mechanism involving gas-phase chemistry, aqueous-phase chemistry, and mass transport.     

Morphological and chemical composition characteristics of summertime atmospheric particles collected at Tokchok Island,Korea

Determination of the chemical compositions of atmospheric single particles in the Yellow Sea region is critical for evaluating the environmental impact caused by air pollutants emitted from mainland China and the Korean peninsula. After ambient aerosol particles were collected by the Dekati PM10 cascade impactor on July 17–23, 2007 at Tokchok Island (approximately 50 km west of the Korean coast nearby Seoul), Korea, overall 2000 particles (on stage 2 and 3 with cut-off diameters of 2.5–10 μm and 1.0–2.5 μm, respectively) in 10 samples were determined by using low-Z particle electron probe X-ray microanalysis. X-ray spectral and secondary electron image (SEI) data showed that soil-derived and sea-salt particles which had reacted or were mixed with SO₂ and NO_x (or their acidic products) outnumbered the primary and “genuine” ones (59.2% vs. 19.2% in the stage 2 fraction and 41.3% vs. 9.9% in the stage 3 fraction). Moreover, particles containing nitrate in the secondary soil-derived species greatly outnumbered those containing sulfate. Organic particles, mainly consisting of marine biogenic species, were more abundant in the stage 2 fraction than in the stage 3 fraction (11.6% vs. 5.1%). Their relative abundance was greater than the sum of carbon-rich, K-containing, Fe-containing, and fly ash particles, which exhibited low frequencies in all the samples. In addition, many droplets rich in C, N, O, and S were observed. They tended to be small, exhibiting a dark round shape on SEI, and generally included 8–20 at.% C, 0–12 at.% N, 60–80 at.% O, and 4–10 at.% S (sometimes with <3 at.% Mg and Na). They were attributed to be a mixture of carbonaceous matter, H₂SO₄, and NH₄HSO₄/(NH₄)₂SO₄, mostly from the reaction of atmospheric SO₂ with NH₃ under high relative humidity. The analysis of the relationship between the aerosol particle compositions and 72-h backward air-mass trajectories suggests that ambient aerosols at Tokchok Island are strongly affected not only by seawater from the Yellow Sea but also by anthropogenic pollutants emitted from China and the Seoul–Incheon metropolis, resulting in the dominance of complex secondary aerosol particles.     

Investigating the chemical nature of humic-like substances (HULIS) in North American atmospheric aerosols by liquid chromatography tandem mass spectrometry

The high-molecular weight water-soluble organic compounds present in atmospheric aerosols underwent functional-group characterization using liquid chromatography tandem mass spectrometry (LC-MS/MS), with a focus on understanding the chemical structure and origins of humic-like substances (HULIS) in the atmosphere. Aerosol samples were obtained from several locations in North America at times when primary sources contributing to organic aerosol were well-characterized: Riverside, CA, Fresno, CA, urban and peripheral Mexico City, Atlanta, GA, and Bondville, IL. Chemical analysis targeted identification and quantification of functional groups, such as aliphatic, aromatic, and bulk carboxylic acids, organosulfates, and carbohydrate-like substances that comprise species with molecular weights (MW) 200–600 amu. Measured high-MW functional groups were compared to modeled primary sources with the purpose of identifying associations between aerosol sources, high-MW aerosol species, and HULIS. Mobile source emissions were linked to high-molecular weight carboxylic acids, especially aromatic acids, biomass burning was associated with carboxylic acids and carbohydrate-like substances, and secondary organic aerosol (SOA) correlated well with the total amount of HULIS measured, whereas organosulfates showed no correlation with aerosol sources and exhibited unique spatial trends. These results suggested the importance of motor vehicles, biomass burning, and SOA as important sources of precursors to HULIS. Structural characteristics of atmospheric HULIS were compared to terrestrial humic and fulvic acids and revealed striking similarities in chemical structure, with the exception of organosulfates which were unique to atmospheric HULIS.     

Mineral aerosols from western India: Temporal variability of coarse and fine atmospheric dust and elemental characteristics

Size-segregated aerosol samples (PM_2.5 and PM₁₀) were collected during Jan–Dec-2007 from a high-altitude site located in a semi-arid region (Mt. Abu, 24.6 °N, 72.7 °E, 1680 m asl) in order to asses the temporal variability in the abundance of atmospheric mineral dust and its elemental composition over western India. The mass concentrations of fine (PM_2.5) and coarse (PM_10–2.5) mode aerosols varied from 1.6 to 46.1 and 2.3 to 102 μg m^?3 respectively over the annual seasonal cycle; with dominant and uniform contribution of mineral dust (60–80%) in the coarse mode relative to large temporal variability (11–75%) observed in the fine mode. The coarse mass fraction shows a characteristic increase with the wind speed during summer months (Mar to Jun); whereas fine aerosol mass and its elemental composition exhibit conspicuous temporal pattern associated with north-easterlies during wintertime (Oct–Feb). The Fe/Al weight ratio in PM_2.5 ranges from 0.5 to 1.0 during winter months. The relative enrichment of Fe in fine mode, compared to the crustal ratio of 0.44, is attributed to the down-wind advective transport of combustion products derived from large-scale biomass burning, industrial and automobile emission sources located in the Indo-Gangetic Plain (northern India). In contrast, Ca/Al and Mg/Al weight ratios show relative enrichment of Ca and Mg in the coarse mode; indicating their dominant contribution from carbonate minerals. This has implication to efficient neutralization of atmospheric acidic species (SO₄^2? and NO₃^?) by mineral dust over western India.     

Sampling artefacts,concentration and chemical composition of fine water-soluble organic carbon and humic-like substances in a continental urban atmospheric environment

Water-soluble organic carbon (WSOC) and atmospheric humic-like substances (HULIS) were investigated for urban PM2.5-fraction aerosol samples, which were collected with the tandem filter method on quartz fibre filters over a non-heating spring season. Sampling artefacts were of importance for all organic chemical fractions, and the back-to-front-filter concentration ratios were on average 28% for WSOC and 17% for HULIS and organic carbon (OC). The difference in the ratios indicates that the water-soluble organics play a more important role in adsorptive artefacts than the organic matter (OM) in general. The results emphasize the need for an appropriate sampling and/or correction method for measuring particulate organic substances in urban environments. The corrected atmospheric concentration of HULIS, obtained by subtracting the back-filter from the front-filter data, was on average 2 μg m⁻³; which represented 6% of the mean PM2.5 particulate mass, and it made up 45% of the secondary OC. The HULIS carbon accounted for 20% of the OC and 62% of the WSOC, while WSOC made up 32% of OC. The major element composition of HULIS, expressed in molar ratios, was C:H:O:N=22:32:10:1. The molar H/C ratio of 1.49 implies the presence of unsaturated organic compounds, although these were depleted in comparison with rural aerosol or standard fulvic acids. The molar O/C ratio of 0.47 indicates the existence of oxygenated functional groups; comparison to rural aerosol suggests that the (fresh) urban-type aerosol is less oxidized (and, therefore, less water soluble as well) than the rural one. The OM/OC mass conversion factor for the isolated (water-soluble) HULIS was derived to be 1.81. It was inferred from comparisons with published data that there are substantial differences in abundance and chemical composition of HULIS for different environments.     

Influence of the surface microlayer on atmospheric deposition of aerosols and polycyclic aromatic hydrocarbons

Atmospheric dry deposition is an important process for the introduction of aerosols and pollutants to aquatic environments. The objective of this paper is to assess, for the first time, the influence that the aquatic surface microlayer plays as a modifying factor of the magnitude of dry aerosol deposition fluxes. The occurrence of a low surface tension (ST) or a hydrophobic surface microlayer has been generated by spiking milli-Q water or pre-filtered seawater with a surfactant or octanol, respectively. The results show that fine mode (<2.7 μm) aerosol phase PAHs deposit with fluxes 2–3 fold higher when there is a low ST aquatic surface due to enhanced sequestration of colliding particles at the surface. Conversely, for PAHs bound to coarse mode aerosols (>2.7 μm), even though there is an enhanced deposition due to the surface microlayer for some sampling periods, the effect is not observed consistently. This is due to the importance of gravitational settling for large aerosols, rendering a lower influence of the aquatic surface on dry deposition fluxes. ST (mN m⁻¹) is identified as one of the key factor driving the magnitude of PAH dry deposition fluxes (ng m⁻² d⁻¹) by its influence on PAH concentrations in deposited aerosols and deposition velocities (v_d, cm s⁻¹). Indeed, v_d values are a function of ST as obtained by least square fitting and given by Ln(v_d)=−1.77 Ln(ST)+5.74 (r²=0.95) under low wind speed (average 4 m s⁻¹) conditions.     

Carbon content of atmospheric aerosols in a residential area during the wood combustion season in Sweden

Carbonaceous aerosol particles were observed in a residential area with wood combustion during wintertime in Northern Sweden. Filter samples were analyzed for elemental carbon (EC) and organic carbon (OC) content by using a thermo-optical transmittance method. The light-absorbing carbon (LAC) content was determined by employing a commercial Aethalometer and a custom-built particle soot absorption photometer. Filter samples were used to convert the optical signals to LAC mass concentrations. Additional total PM₁₀ mass concentrations and meteorological parameters were measured. The mean and standard deviation mass concentrations were 4.4±3.6 μg m⁻³ for OC, and 1.4±1.2 μg m⁻³ for EC. On average, EC accounted for 10.7% of the total PM₁₀ and the contribution of OC to the total PM₁₀ was 35.4%. Aethalometer and custom-built PSAP measurements were highly correlated (R²=0.92). The hourly mean value of LAC mass concentration was 1.76 μg m⁻³ (median 0.88 μg m⁻³) for the winter 2005–2006. This study shows that the custom-built PSAP is a reliable alternative for the commercial Aethalometer with the advantage of being a low-cost instrument.     

Sampling errors in the study of acid gases and anion species in atmospheric aerosols

Atmospheric acid aerosols were sampled by two annular denuder systems (ADS) and a micro-orifice uniform deposit impactor (MOUDI) at a traffic site in central Taiwan. Theoretical analysis showed that the relative artifact for HNO₃ gas sampling was about 0.53 when the initial HNO₃ concentration was under 0.2 µg/m³ and should be considered carefully. The concentrations of gaseous acid at the traffic sampling site were higher than those in the other study. The size distributions of acid aerosols were unimodal for Cl^-, NO₂^-, and NO₃^-, and bimodal for SO₄^2-. The dominant acid ions in particles less than 18 µm were SO₄^2-, NO₃^-, NO₂^- and Cl^-.     

Changes in elemental composition and mass of atmospheric aerosol pollution between 1996 and 2002 in a Central European city

Median atmospheric concentrations of Pb, Br, S, As, Se, and particulate matter (PM) decreased, and median concentrations of Sb, Cu, Zn, Fe, Ca, Cr and Ba increased in urban aerosol in downtown Budapest between 1996 and 2002. The changes in Pb and Br concentrations were unambiguously attributed to the phasing out of leaded gasoline. The increments were mainly related to and explained by non-exhaust vehicular emissions. The mechanical wear of asbestos-free brake linings of road vehicles contributed to the concentration of Cu and Sb on average by 69% and 66%, respectively in the PM10 size fraction. Tire rubber abrasion was a major source for atmospheric Zn; on average, non-crustal sources accounted for 67% of Zn in the PM10 size fraction. Contribution of the tire wear component to the PM10 mass was estimated to be 6% at most, while its contribution to organic aerosol was of the order of 15%.     

Seasonal variations in the chemical composition of particulate matter: a case study in the Po Valley. Part I: macro-components and mass closure

The seasonal variability in the mass concentration and chemical composition of atmospheric particulate matter (PM₁₀ and PM_2.5) was studied during a 2-year field study carried out between 2010 and 2012. The site of the study was the area of Ferrara (Po Valley, Northern Italy), which is characterized by frequent episodes of very stable atmospheric conditions in winter. Chemical analyses carried out during the study allowed the determination of the main components of atmospheric PM (macro-elements, ions, elemental carbon, organic matter) and a satisfactory mass closure was obtained. Accordingly, chemical components could be grouped into the main macro-sources of PM: soil, sea spray, inorganic compounds from secondary reactions, vehicular emission, organics from domestic heating, organics from secondary formation, and other sources. The more significant seasonal variations were observed for secondary inorganic species in the fine fraction of PM; these species were very sensitive to air mass age and thus to the frequency of stable atmospheric conditions. During the winter ammonium nitrate, the single species with the highest concentration, reached concentrations as high as 30 μg/m³. The intensity of natural sources was fairly constant during the year; increases in natural aerosols were linked to medium and long-range transport episodes. The ratio of winter to summer concentrations was roughly 2 for combustion product, close to 3 for secondary inorganic species, and between 2 and 3 for organics. The winter increase of organics was due to poorer atmospheric dispersion and to the addition of the emission from domestic heating. A similar winter to summer ratio (around 3) was observed for the fine fraction of PM.